Abstract: Compared to ecosystem conservation in territorial seas, protecting the open ocean has peculiar geopolitical, economic and scientific challenges. One of the major obstacle is defining the boundary of an open ocean Marine Protected Area (MPA). In contrast to coastal ecosystems, which are mostly constrained by topographic structures fixed in time, the life of marine organisms in the open ocean is entrained by fluid dynamical structures like eddies and fronts, whose lifetime occurs on ecologically-relevant timescales. The position of these highly dynamical structures can vary interannually by hundreds of km, and so too will regions identified as ecologically relevant such as the foraging areas of marine predators. Thus, the expected foraging locations suggested from tracking data cannot be directly extrapolated beyond the year in which the data were collected. Here we explore the potential of Lagrangian methods applied to multisatellite data as a support tool for a MPA proposal by focusing on the Crozet archipelago oceanic area (Indian Sector of the Southern Ocean). By combining remote sensing with biologging information from a key marine top predator (Eudyptes chrysolophus, or Macaroni penguin) of the Southern Ocean foodweb, we identify a highly dynamic branch of the Subantarctic front as a foraging hotspot. By tracking this feature in historical satellite data (1993–2012) we are able to extrapolate the position of this foraging ground beyond the years in which tracking data are available and study its spatial variability.

Abstract: Current understanding of mercury (Hg) behavior in the atmosphere contains significant gaps. Some key characteristics of Hg processes, including anthropogenic and geogenic emissions, atmospheric chemistry, and air–surface exchange, are still poorly known. This study provides a complex analysis of processes governing Hg fate in the atmosphere involving both measured data from ground-based sites and simulation results from chemical transport models. A variety of long-term measurements of gaseous elemental Hg (GEM) and reactive Hg (RM) concentration as well as Hg wet deposition flux have been compiled from different global and regional monitoring networks. Four contemporary global-scale transport models for Hg were used, both in their state-of-the-art configurations and for a number of numerical experiments to evaluate particular processes. Results of the model simulations were evaluated against measurements. As follows from the analysis, the interhemispheric GEM gradient is largely formed by the prevailing spatial distribution of anthropogenic emissions in the Northern Hemisphere. The contributions of natural and secondary emissions enhance the south-to-north gradient, but their effect is less significant. Atmospheric chemistry has a limited effect on the spatial distribution and temporal variation of GEM concentration in surface air. In contrast, RM air concentration and wet deposition are largely defined by oxidation chemistry. The Br oxidation mechanism can reproduce successfully the observed seasonal variation of the RM ∕ GEM ratio in the near-surface layer, but it predicts a wet deposition maximum in spring instead of in summer as observed at monitoring sites in North America and Europe. Model runs with OH chemistry correctly simulate both the periods of maximum and minimum values and the amplitude of observed seasonal variation but shift the maximum RM ∕ GEM ratios from spring to summer. O3 chemistry does not predict significant seasonal variation of Hg oxidation. Hence, the performance of the Hg oxidation mechanisms under study differs in the extent to which they can reproduce the various observed parameters. This variation implies possibility of more complex chemistry and multiple Hg oxidation pathways occurring concurrently in various parts of the atmosphere.

Abstract: Under the framework of the GMOS project (Global Mercury Observation System) atmospheric mercury monitoring has been implemented at Concordia Station on the high-altitude Antarctic plateau (75°06′ S, 123°20′ E, 3220 m above sea level). We report here the first year-round measurements of gaseous elemental mercury (Hg(0)) in the atmosphere and in snowpack interstitial air on the East Antarctic ice sheet. This unique data set shows evidence of an intense oxidation of atmospheric Hg(0) in summer (24-hour daylight) due to the high oxidative capacity of the Antarctic plateau atmosphere in this period of the year. Summertime Hg(0) concentrations exhibited a pronounced daily cycle in ambient air with maximal concentrations around midday. Photochemical reactions and chemical exchange at the air–snow interface were prominent, highlighting the role of the snowpack on the atmospheric mercury cycle. Our observations reveal a 20 to 30 % decrease of atmospheric Hg(0) concentrations from May to mid-August (winter, 24 h darkness). This phenomenon has not been reported elsewhere and possibly results from the dry deposition of Hg(0) onto the snowpack. We also reveal the occurrence of multi-day to weeklong atmospheric Hg(0) depletion events in summer, not associated with depletions of ozone, and likely due to a stagnation of air masses above the plateau triggering an accumulation of oxidants within the shallow boundary layer. Our observations suggest that the inland atmospheric reservoir is depleted in Hg(0) in summer. Due to katabatic winds flowing out from the Antarctic plateau down the steep vertical drops along the coast and according to observations at coastal Antarctic stations, the striking reactivity observed on the plateau most likely influences the cycle of atmospheric mercury on a continental scale.

Abstract: During atmospheric mercury and ozone depletion events in the springtime in polar regions gaseous elemental mercury and ozone undergo rapid declines. Mercury is quickly transformed into oxidation products, which are subsequently removed by deposition. Here we show that such events also occur during Antarctic winter over sea ice areas, leading to additional deposition of mercury. Over four months in the Weddell Sea we measured gaseous elemental, oxidized, and particulate-bound mercury, as well as ozone in the troposphere and total and elemental mercury concentrations in snow, demonstrating a series of depletion and deposition events between July and September. The winter depletions in July were characterized by stronger correlations between mercury and ozone and larger formation of particulate-bound mercury in air compared to later spring events. It appears that light at large solar zenith angles is sufficient to initiate the photolytic formation of halogen radicals. We also propose a dark mechanism that could explain observed events in air masses coming from dark regions. Br2 that could be the main actor in dark conditions was possibly formed in high concentrations in the marine boundary layer in the dark. These high concentrations may also have caused the formation of high concentrations of CHBr3 and CH2I2 in the top layers of the Antarctic sea ice observed during winter. These new findings show that the extent of depletion events is larger than previously believed and that winter depletions result in additional deposition of mercury that could be transferred to marine and terrestrial ecosystems.

Abstract: Limited studies have been conducted on mercury concentrations in the polar cryosphere and the factors affecting the distribution of mercury within sea ice and snow are poorly understood. Here we present the first comprehensive seasonal study of elemental and total mercury concentrations in the Antarctic sea ice environment covering data from measurements in air, sea ice, seawater, snow, frost flowers, and brine. The average concentration of total mercury in sea ice decreased from winter (9.7 ng L–1) to spring (4.7 ng L–1) while the average elemental mercury concentration increased from winter (0.07 ng L–1) to summer (0.105 ng L–1). The opposite trends suggest potential photo- or dark oxidation/reduction processes within the ice and an eventual loss of mercury via brine drainage or gas evasion of elemental mercury. Our results indicate a seasonal variation of mercury species in the polar sea ice environment probably due to varying factors such as solar radiation, temperature, brine volume, and atmospheric deposition. This study shows that the sea ice environment is a significant interphase between the polar ocean and the atmosphere and should be accounted for when studying how climate change may affect the mercury cycle in polar regions.